Chapter 2: Entropy and Temperature

Fundamental Assumption
The fundamental assumption of thermal physics is that a closed system is equally likely to be
in any of the quantum states accessible to it. All accessible quantum states are assumed to
be equally probable- there is no reason to prefer some accessible states over other accessible
states.
A close system will have constant energy, constant number of particles, constant volume,
and constant values of all external parameters that may influence the system.

Probability
Suppose we have a closed system that we know is equally likely to be in any of the g accessible
quantum states. Let s be a general state label (and not one-half of the spin excess). The
probability P(s) of finding the system in this state is

P (s) = 1/g (1)

if the state s is accessible and P(s) = 0 otherwise, consistent with the fundamental assump-
tion.
The sum of the probability over all states is always equal to unity.
X
P (s) = 1 (2)
s

Suppose that the physical property X has the value X(s) when the system is in the state
s. Then the average of the observations of the quantity X taken over a system described by
the probabilities P(s) is X
< X >= X(s)P (s) (3)
s

This equation defines the average value of X. Here P(s) is the probability that the system is
in the state s. For a close system the average value of X is
X
< X >= X(s)(1/g) (4)
s

because now all g accessible states are equally likely. The average in (4) is an elementary
example of what may be called an ensemble average: we imagine g similar systems, one
in each accessible quantum state. Such a group of systems constructed alike is called an
ensemble of systems. The average of any property over the group is called the ensemble
average of that property.
An ensemble of systems is composed of many systems all constructed alike.
Each system in the ensemble is a replica of the actual system in one of the quantum states
accessible to the system. If there are g accessible states, then there will be g systems in the

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ensemble, one system for each state. Every quantum state accessible to the actual system is
represented in the ensemble by one system in a stationary quantum state. We assume that
the ensemble represents the real system-this is implied in the fundamental assumption.

Most Probable Configuration

Let two systems S1 and S2 be brought into contact so that energy can be transferred freely
from one to the other. This is called thermal contact. The two systems in contact form a
larger closed system S = S1+S2 with constant energy U = U1 + U2.
We first solve in detail the problem of thermal contact between two spin systems, 1 and
2, in a magnetic field which is introduced in order to define the energy. The numbers N1,
N2 may be different and the values of the spin excess 2S1, 2S2 may be different for the two
systems. We assume that the quantum states of the total system S can be represented by
a combination of any state of S1 with any state of S2. We keep N1, N2 constant, but the
values of the spin excess are allowed to change. The spin excess of a state of the combined
system will be denoted by 2s where s = s1 + s2. The energy of the combined system is
directly proportional to the total spin excess:

U (s) = U1 (s1 ) + U2 (s2 ) = −2mB(s1 + s2 ) = −2mBs (5)

We assume that the energy splittings between adjacent energy levels are equal to 2mB
in both systems so that the magnetic energy given up by system 1 when one spin is reversed
can be taken up by the reversal of one spin of system 2 in the opposite sense. The value of
s = s1 + s2 is constant because the total energy is constant, but when the two systems are
brought into thermal contact a redistribution is permitted in the separate values of s1, s2
and thus in the energies U1, U2.
The multiplicity function g(N,s) of the combined system S is related to the product of
the multiplicity functions of the individual systems S1 and S2 by the relation:
X
g(N, s) = g1 (N1 , s1 )g2(N2 , s − s1 ) (6)
s1

The range of s1in the summations is from -1/2N1 to 1/2N1 if N1¡N2. The result is a
sum of products that will be a maximum for some value of s1, say sˆ1 . The configuration
for which g1g2 is a maximum is called the most probable configuration, the number of
states in it is
g1 (N1 , sˆ1 )g2(N2 , s − sˆ1 ) (7)
If the systems are large, the maximum with respect to changes in s1 will be extremely
sharp, postulate that it is a general property of all large systems.
The important result follows that the values of the average physical properties of a
large system in thermal contact with another large system are accurately described by the
properties of the most probable configuration, the configuration for which the number of
accessible states is a maximum. Such average values (used in either of these two senses) are
called thermal equilibrium values.
Because of the sharp maximum, we may replace the average of a physical quantity over
all accessible configurations (6) by an average over only the most probable configuration (8).

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Ex. Two spin systems in thermal contact
2s21 2(s − s1 )2
 
g1 (N1 , s1 )g2(N2 , s − s1 ) = g1 (0)g2 (0)exp − − (8)
N1 N2
This product gives the number of states accessible to the combined system when the spin
excess of the combined system is 2s and the spin excess of the first system is 2s1.
Use the property that the maximum of log y(x) occurs at the same value of x as the
maximum of y(x).
2s21 2(s − s1 )2
log g1 (N1 , s1 )g2(N2 , s − s1 ) = log g1 (0)g2 (0) − − (9)
N1 N2
The first derivative gives you the extremum and the second derivative lets you know it’s a
maximum. The most probable configuration of the combined system is satisfied:
s1 s − s1 s2
= = (10)
N1 N2 N2
To find the number of states in the most probable configuration:
(g1g2)max = g1 (sˆ1 )g2(s − sˆ1 = g1 (0)g2(0)exp(−2s2 /N ) (11)
The number of states in a configuration of deviation δ from the equilibrium is
2δ 2 2δ 2
 
g1 (N1 , sˆ1 + δ)g2(N2 , sˆ2 − δ) = (g1g2)max exp − − (12)
N1 N2

Thermal Equilibrium
X
g(N, U ) = g1 (N1 , U1 )g2 (N2 , U − U1 ) (13)
U1
The largest term in the sum governs the properties of the total system in thermal equi-
librium. For an extremum it is necessary that the differential of g(N,U) be zero for an
infinitesimal exchange of energy:
   
∂g1 ∂g2
dg = g2 dU1 + g2 dU2 = 0; dU1 + dU2 = 0 (14)
∂U1 N1 ∂U2 N2
We divide by g1g2 and use the result dU2 = -dU1 to obtain the thermal equilibrium
condition:    
∂ log g1 ∂ log g2
= (15)
∂U1 N1 ∂U2 N2
We define the quantity σ called the entropy by:
σ(N, U ) ≡ log g(N, U ) (16)
So:    
∂σ1 ∂σ2
= (17)
∂U1 N1 ∂U2 N2
This is the condition for thermal equilibrium for two systems in thermal contact. Here N1
and N2 may symbolize not only the numbers of particles, but all constraints on the systems.

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Temperature
In thermal equilibrium, the temperatures of the two systems are equal.
 
1 ∂σ
= (18)
τ ∂U N
 
1 ∂σ
= kB (19)
T ∂U N

Entropy
The entropy is defined as the logarithm of the number of states accessible to the system. In
classical thermodynamics the entropy S is defined by
 
1 ∂S
= (20)
T ∂U N

As a consequence, we see that S and σ are connected by a scale factor:

S = kb σ (21)

S is called the conventional entropy. The more states that are accessible the greater the
entropy.
Consider the total entropy change when we remove a positive amount of energy from 1
and add the same amount of energy to 2. The total entropy change is
     
∂σ1 ∂σ2 1 1
∆σ = (−∆U ) + (∆U ) = − + ∆U (22)
∂U1 N1 ∂U2 N2 τ1 τ2

Law of Increase of Entropy

We can show that the total entropy always increases when two systems are brought into
thermal contact. Since all terms are positive in the summation, the law of increase of
entropy is a well-defined operation.

(g1 g2 )max = g1 (Û1 )g2 (U − Û1 ) (23)

The statement
σf inal ≈ log(g1 g2 )max ≥ σinintial =≈ log(g1 g2 )0 (24)
is a statement of the law of increase of entropy: the entropy of a closed system tends to
remain constant or to increase when a constraint internal to the system is removed.
For a large system there will never occur spontaneously significant differences between the
actual value of the entropy and the value of the entropy of the most probable configuration
of the system.

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Laws of Thermodynamics
Zeroth Law If two systems are in thermal equilibrium with a third system, they must be
in thermal equilibrium with each other.
First Law Heat is a form of energy. This law is no more than a statement of the principle
of conservation of energy.
Second Law Statistical Statement: law of increase of entropy, applicable when a con-
straint internal to a closed system is removed. ”If a closed system is in a configuration that
is not the equilibrium configuration, the most probable consequence will be that the entropy
of the system will increase monotonically in successive instants of time”.
The traditional thermodynamic statement is the Kelvin-Planck formulation of second law
of thermodynamics: ”It is impossible for any cyclic process to occur whose sole effect is the
extraction of heat from a reservoir and the performance of an equivalent amount of work.”
An engine that violates the second law by extracting the energy of one heat reservoie is said
to be performing perpetual motion of the second kind.
Third Law The entropy of a system approaches a constant value as the temperature
approaches zero.

Entropy as a logarithm
The entropy of two independent systems is the sum of the separate entropies. The entropy is
entirely insensitive to the precision δU with which the energy of a closed system is defined.

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Summary
1. The fundamental assumption is that a closed system is equally likely to be in any of the
quantum states accessible to it.
2. If P(s) is the probability that a system is in the state s, the average value of a quantity
X is X
< X >= X(s)(1/g) (25)
s

3. An ensemble of systems is composed of very many systems all constructed alike.

4. The number of accessible states of the combined systems 1 and 2 is
X
g(s) = g1 (s1 )g2(s − s1 ) (26)
s

5. The entropy σ(N, U ) ≡ log g(N, U ). The relation S = kB σ connects the conventional
entropy S with the fundamental entropy σ.
6. The fundamental temperature τ is defined by
 
1 ∂σ
= (27)
τ ∂U N,V

The relation τ = kB T connects the fundamental temperature and the conventional temper-
ature.
7. The law of increase of entropy states that the entropy of a closed system tends to
remain constant or to increase when a constraint internal to the system is removed.
8. The thermal equilibrium values of the physical properties of a system are defined
as averages over all states accessible when the system is in contact with a large system
or reservoir. If the first system also is large, the thermal equilibrium properties are given
accurately by consideration of the states in the most probable configuration alone.